Copolymers of dialkenyl monochloromethanephosphonate



United States Patent COPOLYNIERS OF DIALKENYL MONOCI-ILORO-METHANEPHOSPHONATE Arthur Dock Fon Toy, Park Forest, and Kenneth H.Rattenbury, South Chicago Heights, 111., assignors to Victor ChemicalWorks, a corporation of Illinois No Drawing. Application January 27,1955 Serial No. 484,584

17 Claims. (Cl. 26045.4)

This invention relates to copolymers of dialkenylmonochloromethanephosphonates and materials copolymerizable therewith.More specifically, this invention relates to flame-resistant copolymersof diallyl and dimethallyl monochloromethanephosphonates and materialscopolymerizable therewith.

This application is a continuation-in-part of copending applicationSerial No. 302,835, Patent 2,714,100, filed August 5, 1952.

It has been found that many commonly used flammable, polymerizablemonomers, when copolymerized with a dialkenylmonochloromethanephosphonate are improved in physical quality and at thesame time rendered flame-resistant. This unexpected flame-resistance isachieved by mixing as little as ten percent of the phosphonate monomerwith the flammable monomer followed by heating in the presence of asmall quantity of a catalyst (i.e., organic peroxide). The variousproportions of reactants and catalyst and the conditions of time andtemperature suitable for producing the copolymers of this invention maybe varied over a considerable range as will be shown in the followingexamples.

The dialkenyl monochloromethanephosphonates may be prepared by reactingan alkenyl alcohol with methanephosphorus oxydichloride in the presenceof tertiary amines such as pyridine and triethylamine with or without aninert solvent such as benzene, hexane, etc.

The copolymerizable materials that may be copolymerized with thedialkenyl monochloromethanephosphonates are numerous and include vinylacetate, methyl methacrylate, and various diallyl esters of phthalicacid and saturated aliphatic dicarboxylic acids such as oxalic,succinic, sebacic, adipic and the like.

In addition to the above-described copolymerizable materials containingethylenic unsaturation that may be polymerized with the dialkenylmonochloromethanephosphonate, polymerizable polyesters may be employedthat are characterized by unsaturated carbon-to-carbon bonds and henceare capable of undergoing polymerization during curing without theliberation of water. Three groups of compounds which may be used in thepreparation of these unsaturated polyesters are as follows: (1) acidssuch as maleic, fumar'ic, itaconic, phthalic and the like; (2) alcoholsor glycols such as allyl alcohol, ethylene glycol and diethylene glycol;(3) unsaturated hydrocarbons such as styrene, cyclopentadiene and thelike. For example, the polyesters disclosed in United States Patent No.2,255,313 are illustrative of these unsaturated polyesters. Certaincommercial polyesters such as the Laminacs sold by American CyanamidCompany also form satisfactory copolymers. The specific Laminacshereinafter referred to are maleic anhydride-ethylene glycol typepolyesters containing styrene. For example Laminac No. 4201 (partiallypolymerized unsaturated polyester such as generally described in US.Pat. No. 2,443,736, containing an alkenyl ary] cross-linking agent, suchas diallyl phthalate, and the reaction product of an alpha, betaethylenically unsaturated polycarboxylic acid, such as maleic or fumaricacid, a saturated polycarboxylic acid free of non-benzoid unsaturation,such as phthalic acid, and at least one glycol, such as ethylene glycoland/or diethylene glycol), produced by American Cyanamid Company, may beused.

The following examples illustrate some of the copolymers of theinvention. In all cases, unless otherwise stated, the designated amountsof the chloromethanephosphonate and selected monomer were placed in asmall bottle and the requisite amount of catalyst added. The bottle wasthen flushed with nitrogen, stopperecl tightly, and placed in an oilbath for 16 hours at C. Proportions are parts by weight in all cases.

TABLE I Copolymers of diallyl chloromethanephosphonate with diallylphthalate (DAP) Percent Percent Percent Physical Appearance Flamma- DCMPDAP BlzOz bility, sec.

0 100 2.5 Light yellow, tough solid.. 15 2.5 1 20 80 2.5 1 30 70 2.5 150 50 2.0 1 70 30 1.5 1 90 10 1.3 1

1 See footnote 1, Table II. I See footnote 2, Table II.

TABLE II Copolymers of diallyl chloromethanephosphonate (DCMP) withmethyl methacrylate (MM) Pe cent Percent. Percent Physical AppearanceFlamma- DGMP MM B1201 bility, sec.

15 10 90 0 12 15 20 80 0.14 do 15 30 70 0. 2 Fractured, colorless s 1 505O 0 4 Light yellow, tough solid. 1 70 30 O 6 1 9O 10 0 9 1 1 Benzoylperoxide catalyst, based on total weight.

2 Flammability in all cases was measured by heating a piece of theproduct GM to la in diameter) for 15 seconds in the tip of a 1" to 1%blue flame, and then removing the flame and determining how long thepiece continued to burn. The recorded time in each case is the longestof three tests. Flame resistance is deemed satisfactory if the burningtime is less than 15 seconds.

TABLE III 3 TABLE IV copolymers of diallyl chloromethanephosphonate withvinyl acetate (VA) 1 Percent Percent Percent Physical Appearance Flarnma- DCMP VA B1202 bility O 100 0. 2 Bubbly artgum. 15 sec. 10 90 0.2Cloudy, tough solid 2 sec. 20 80 0. 4 d 1 sec. 30 70 0.5 1 sec. 50 500.6 70 30 0. 7 (Artgums not 90 10 g 0.9 tested.)

1 Polymerization at 5570 C. for 20 hours.

TABLE V copolymers of diallyl chloromethanephosphonate and Laminate 4201Copolymers of diallyl chloromethanephosphonate with Laminac 4150 PercentPercent Percent Physical Appearance Flammabil- DCMP Laminac H.202 ity100 0.5 Clear, yellow, tough solid 15 sec. 10 90 0.5 15 sec. 20 80 0. 62 sec. 30 70 0.9 4 sec. 50 50 1. 1

not te ted. 70 30 1.3 do. Do. 0 10 l. Clear, yellow, tough solid 1 sec.

Similar samples of Laminac 4116 and a mixture of Laminac 4116 (75%) andLaminac 4734 (25%) were polymerized with diallylchloromethanephosphonate and were found to produce satisfactoryflame-resistant solids in all compositions containing at least 20% ofthe phosphonate monomer.

It can be seen from the above examples that for the diallylchloromethanephosphonate the degree of flame resistance of'itscopolymers generally increases as the percentage of phosphonateincreases. As little as ten percent gives satisfactory resistance insome cases. The level at which the copolymer becomes self-extinguishingvaries somewhat with the different nonphosphonate mono-. mers but isgenerally in the range of -30%.

This is in sharp contrast to the behavior of the dimethallylchloromethanephosphonate. .This compound when polymerized individuallyburns readily. Even when copolymerized with 50% of the diallyl ester theI proof resin is produced in many instances.

4 TABLE vn Copolymers of dimethallyl chloromethanephosphonate withdiallyl phthalate Percent Percent Percent Physical Appearance Flammabil-DCMP DAP B1202 ity, sec.

10 90 3. 0 Light yellow, frac- 1 20 3. 0 1 30 70 2. 5 1 90 10 1. 8 15TABE VIII Copolymers of dimethallyl chloromethaxephosphonate withLaminac 4201 Percent Percent Percent Physical Appearance Flammabil- DCMPLaminac B1102 ity, 56c.

10 90 0. 5 Light yellow, tough solid 15 20 80 0.6 Light yellow,fractured solid 2 30 70 0.8 .do 2 90 10 1.8 Light yellow, tough solid 15TABLE IX Copolymers of dimethallyl chloromethanephosphonate with methylmethacrylate Percent Percent Percent Physical Appearance Flammabil- DCMPMM 13,202 ity, we.

10 90 0.12 Colorless, bubbly tough solid 15 20 80 0.14 do 15 30 70 0.22do 7 90 10 1. 3 Light yellow, tough solid 15 TABLE X copolymers ofdimethallyl chloromethanephosphonate with vinyl acetate 1 PercentPercent Percent Physical Appearance Flammabil- DCM P A B .201 iii-Y 1090 0. 2 Cloudy, tough solid- 3 sec.

20 80 0. 4 Fractured. tough solid 2 sec.

30 70 0.5 Cloudy, tough solid... 1 sec.

90 1O 1. 3 Colorless artgum Not tested.

1 Polymerization at 5570 for 20 hours.

The conditions of time and temperature at which polymerization takesplace may be varied over quite a wide range and still producesatisfactory flame-resistant products. Thus, in the following examplesthe monomer mixture was heated at 70-85 C. until the copolymer gelled Iafter which the temperature was raised to complete/the polymerization ina short time.

EXAMPLE I Ten parts of diallyl chloromethanephosphonate and 90 parts ofdiallyl phthalate were mixed with 2.5% benzoyl peroxide in a glassbottle which was then flushed with nitrogen and sealed. The bottle wasput in an oil bath at C. and held there for 2 hours and 45 minutes (onehour past the gelation stage). It was then held at 110 C. for 2 hours,which completed the polymerization, to give a light yellow, tough solidwhich was self-extinguishing.

EXAMPLE II vThe procedure of Example I was repeated using 10 partsdiallyl chloromethanephosphonate, parts Laminac 4201, and 0.5% catalyst.After heating at 70 C.

for 2 hours and 15 minutes, and C. for 1 hour, a light yellow, tough,sclf'extinguishing solid resulted;

EXAMPLE III Using a similar procedure, 30 parts of diallylchloromethanephosphonate, 70 parts methacrylate and 0.2% catalyst wereheated at 70 C. for 2 hours and 55 minutes, 85 C. for 1 hour and 110 C.for 1 hour. A bubbly, hard, tough, colorless, self-extinguishing solidresulted.

EXAMPLE IV The dimethallyl chloromethanephosphonate ester was used torepeat Examples I-III except that a 20/80 ratio was used with Laminac4201 and the amounts of catalyst were varied slightly. Toughself-extinguishing solids were produced in each case.

The above tables and examples show only copolymers in which at least tenpercent of the phosphonate monomer is included. Copolymers containing aslittle as one percent of the phosphonate may be similarly made toproduce hard, clear products. The advantages to be obtained from thephosphonate, however, will be less at these lower levels.

The invention may be embodied in other specific forms without departingfrom the spirit or essential characteristics thereof. The presentembodiments are, therefore, to be considered in all respects asillustrative and not restrictive, the scope of the invention beingindicated by the appended claims rather than by the foregoingdescription and all changes which come within the meaning and languageof equivalency of the claims are therefore intended to be embracedtherein.

We claim:

1. A flame-resistant copolymer of lower dialkenylmonochloromethanephosphonate and materials containing ethylenicunsaturation copolymerizable therewith.

2. A copolymer of diallyl monochloromethanephosphonate and materialscontaining ethylenic unsaturation copolymerizable therewith.

3. A copolymer of dimethallyl monochloromethanephosphonate and materialscontaining ethylenic unsaturation copolymerizable therewith.

4. A copolymer of 1-90% of a phosphate compound from the classconsisting of diallyl monochloromethanephosphonate and dimethallylmonochloromethanephosphonate and 99-10% of copolymerizable materialcontaining ethylenic unsaturation.

5. A copolymer of l-90% of a lower dialkenylmonochloromethanephosphonate and 99-10% of polymerizable materialcontaining ethylenic unsaturation from the 6 group consisting of methylmethacrylate, vinyl acetate, maleic anhydride-ethylene glycolcondensation product containing styrene, and diallyl esters of a memberof the class consisting of saturated aliphatic dicarboxylic acids andphthalic acid.

6. The copolymer of claim 5 wherein the lower dialkenylmonochloromethanephosphonate is diallyl monochloromethanephosphonate.

7. The copolymer of claim 5 wherein the lower dialkenylmonochloromethanephosphonate is dimethallylmonochloromethanephosphonate.

8. The copolymer of 10-90% lower dialkenyl monochloromethanephosphonateand -10% of diallyl phthalate.

9. The copolymer of 10-90% lower dialkenyl monochloromethanephosphonateand 90-10% of methyl methacrylate.

10. The copolymer of 10-90% lower dialkenyl monochloromethanephosphonateand 90-10% of diallyl succinate.

11. The copolymer of 10-90% lower dialkenyl monochloromethanephosphonateand 90-10% of vinyl acetate.

12. The copolymer of 10-90% lower dialkenyl monochloromethanephosphonateand 90-10% of a maleic anhydride-ethylene glycol condensation productcontaining styrene.

13. The copolymer of 10-90% of diallyl monochloromethanephosphonate and90-10% of diallyl phthalate.

14. The copolymer of 10-90% of diallyl monochloromethanephosphonate and90-10% of methyl methacrylate.

15. The copolymer of 10-90% of diallyl monochloromethanephosphonate and90-10% of vinyl acetate.

16. The copolymer of 10-90% of diallyl monochloromethanephosphonate and90-10% of a maleic anhydrideethylene glycol condensation productcontaining styrene.

17. The copolymer 1090% of dimethallyl monochloromethanephosphonate and90-10% of a maleic anhydride-ethylene glycol condensation productcontaining styrene.

References Cited in the file of this patent UNITED STATES PATENTS2,497,638 Toy Feb. 14, 1950 2,586,884 Toy et al Feb. 26, 1952 2,634,244Simon et al Apr. 7, 1953 2,714,100 Toy July 26, 1955 UNITED STATESPATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 2,918,449 December 221959 Arthur Dock Fon Toy et a1.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction and that the saidLetters Patent should read as corrected below.

Column 1, line 39, for "methanephosphorus" read ohloromethanephosphoruscolumn 6, line 37, after "copolymer" insert of Signed and sealed this4th day of October 1960.

(SEAL) Attest:

KARL H, AXLINE ROBERT C. WATSON Attesting Ofiicer Commissioner ofPatents

1. A FLAME-RESISTANT COPOLYMER OF LOWER DIALKENYLMONOCHLOROMETHANEPHOSPHONATE AND MATERIALS CONTAINING ETHYLENICUNSATURATION COPOLYMERIZABLE THEREWITH